Alkanesulfonate derivatives and their use as insecticides, acaricides or nematicides

ABSTRACT

Disclosed herein is a compound of the formula: ##STR1## wherein Ar is pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, isoquinoline ring or thiazole ring, and those rings may be substituted by 1˜3 of substituents selected from the group consisting of halogen, C.sub. 1 ˜C 4  -alkyl, C 1  ˜C 4  -alkoxy, CF 3  and nitro, 
     R 1  is C 1  ˜C 8  -alkyl; C 1  ˜C 7  -alkyl which is substituted by 1˜3 of F, Cl or Br, C 1  ˜C 4  -alkoxy or C 1  ˜C 4  -alkylthio; C 3  ˜C 7  -cycloalkyl which may be substituted by 1˜4 of F, Cl or methyl; C 3  ˜C 6  -cycloalkylmethyl which may be substituted by 1˜4 of F, Cl, Br or methyl; allyl, propargyl, phenyl or benzyl; R 2  is C 1  ˜C 4  -alkyl which may be substituted by 1˜3 of F or Cl, 
     x is integer of 0, 1 or 2, excepting wherein Ar is pyridine ring which is substituted by R 1  --S(O)x and --O--SO 2  R 2  at 2- and 6-position and the R 1  is C 1  ˜C 7  -alkyl and the pyridine ring is not further substituted or substituted by 1˜3 of halogen.

This application is a division of application Ser. No. 913,319, filed Sept. 30, 1986, now U.S. Pat. No. 4,791,127.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to a compound of the formula: ##STR2## wherein Ar is pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, isoquinoline ring or thiazole ring and those rings may be substituted by 1-3 of substituents selected from the group consisting of halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, CF₃ and nitro,

R¹ is C₁ -C₈ -alkyl; C₁ -C₇ -alkyl which is substituted by 1-3 of F, Cl or Br, C₁ -C₄ - alkoxy or C₁ -C₄ -alkylthio; C₃ -C₇ -cycloalkyl which may be substituted by 1-4 of F, Cl or methyl; C₃ -C₆ -cycloalkylmethyl which may be substituted by 1-4 of F, Cl, Br or methyl; allyl; propargyl; phenyl or benzyl; R² is C₁ -C₄ -alkyl which may be substituted by 1-3 of F or Cl,

x is integer of 0, 1 or 2, excepting wherein Ar is pyridene ring which is substituted by R¹ --S(O)_(x) and -O-SO₂ R² at 2- and 6-positions and the R¹ is C₁ -C₇ -alkyl and the pyridine ring is not further substituted or is substituted by 1˜3 of halogen.

The compounds of the present invention can be utilized as an insecticide, acaricide or nematicide in paddy fields, uplands, orchards, forests or the like.

Certain alkanesulfonate derivatives are known to be useful as an active ingredient of an insecticide or a nematicide.

For example, 3-n-butylthiophenyl methanesulfonate and 3-ethylthiophenyl methanesulfonate are described to be useful as an insecticide in Japanese Patent Publication No. 3898/1968 and Japanese Patent Laid-Open No. 98025/1973, respectively. Further, it is reported in J. Agr. Food Chem. 18(1), 57(1970) that 6-chloro-2-pyridyl methanesulfonate has a nematicidal activity.

Alkanesulfonate derivatives of the prior art have an insufficient insecticidal effect on insect pests which have acquired a resistance to organic phosphate or carbamate insecticides or the like, and on insect pests exhibiting a high susceptibility, so that a compound which can prevent such insects with a low dosage has been desired.

The present inventors have found that a compound having a high insecticidal, acaricidal or nematicidal activity can be obtained by substituting the pyridine, pyridazine, pyrimidine, pyrazine, isoquinoline or thiazole rings, with one alkylthio, alkylsulfin alkylsulfonyl groups as well as with an alkanesulfonyloxy group, as shown by the aforementioned formula (I).

An alkanesulfonate derivative represented by the general formula (I) can be prepared by reacting a compound represented by the general formula: ##STR3## wherein Ar, R¹ and x are as defined above and Y¹ is a hydrogen, alkali or alkaline earth metal atom, or a compound represented by the general formula: ##STR4## wherein Z² is hydrogen, halogen, C₁ ˜C₄ -alkyl which may be substituted by halogen, with a sulfonyl halide represented by the general formula:

    Z.sup.1 --SO.sub.2 --R.sup.2                               (III)

wherein R² is as defined above, and Z¹ is halogen, or a sulfonic acid anhydride represented by the general formula:

    (R.sup.2 SO.sub.2).sub.2 O                                 (IV)

wherein R² is as defined above, in a solvent, if necessary, in the presence of an acid binding agent at a temperature of -10° to 100° C., preferably 0° to 40° C., for 0.5 to 10 hours.

Examples of the solvent to be used include water; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and petroleum benzine; halogenated hydrocarbons such as chloroform and dichloromethane; aprotic polar solvents such as dimethylformamide and dimethylsulfoxide; ethers such as diisopropyl ether, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane; nitriles such as acetonitrile and propionitrile; ketones such as acetone, diisopropyl ketone and methyl ethyl ketone. Examples of the acid binding agent of bases include alkali metal hydroxides such as NaOH and KOH; alkaline earth metal hydroxides such as Ca(OH)₂ and Mg(OH)₂ ; alkali metal hydrides; alkali metal alcoholates such as sodium alcoholate; alkali metal oxides such as Na₂ O and K₂ O; alkali metal carbonates such as soda ash; sodium amide; aliphatic or aromatic tertiary amines such as triethylamine, dialkyl anilines, pyridines. In addition, silver oxide may be used as an acid binding agent.

Furthermore, a phase transfer catalyst, for example, tetra-n-butylammonium bromide or triethylbenzylammonium chloride, may be also used to obtain the objective alkanesulfonate derivatives in a favorable yield.

Alternatively, a compound represented by the general formula (I) wherein x is 1 or 2 can be prepared as follows:

A compound represented by the general formula: ##STR5## wherein Ar, R¹ and R² are as defined above, which corresponds to the general formula (I) wherein x is zero by means of the above-mentioned manner, and then the compound of the formula (V) is treated with an oxidizing agent such as hydrogen peroxide to produce the compound of the formula (I). That is, when the compound represented by the general formula (V) is treated in acetic acid containing 1.0 to 3.0 times by mol as much hydrogen peroxide, preferably at 0° to 60° C. for 3 to 7 hours, a compound represented by the general formula (I) wherein x is 1 can be obtained, while when the compound represented by the general formula (V) is treated in acetic acid containing 2.0 to 5.0 times by mol as much hydrogen peroxide, preferably at 15° to 90° C. for 2 to 24 hours, a compound represented by the general formula (I) wherein x is 2 can be obtained in a high yield. In this treatment, alcohols such as t-butanol, acetone, water or the mixture thereof can be used as a solvent in place of acetic acid.

Examples of the oxidizing agent to be used in oxidizing a compound represented by the general formula (I) wherein x is zero into the corresponding compound of the general formula (I) wherein x is 1 include sodium bromite, organic peroxides, organic halides such as N-bromo-succinimide, bromine, iodine, periodates, nitrogen oxides, ozone, metal oxides, and singlet oxygen as well as hydrogen peroxide. Additionally, this oxidation can be carried out by air or anodic oxidation.

Examples of the oxidizing agents to be used in oxidizing a compound represented by the general formula (I) wherein x is zero or 1 into the corresponding compound represented by the general formula (I) wherein x is 2 include peroxy acid, hydrogen peroxide, halogen, halogenating agents, ozone, oxygen and transition metal catalysts, potassium peroxysulfate, potassium permanganate; dinitrogen tetraoxide sodium metaperiodate, osmium oxide (Os^(VIII)) ruthenium oxide (Ru^(III)), sodium dichromate and nitric acid as well as hydrogen peroxide. Additionally, the oxidation with electrode is possible.

The intermediate represented by the general formula (II), for example, wherein Ar is pyridine, can be prepared by the process indicated in U.S. Pat. No. 3,335,146, which can be also applied to the intermediate represented by the general formula (II) wherein Ar is defined as other than pyridine. Further, the other processes shown by the following Course of Reactions are very effective as an alternative synthesis. ##STR6## In order to obtain the compound (VII) from (VI), an alcohol represented by the formula R³ OH, for example, benzylalcohol is treated by about equivalent mol of sodium hydride in the same solvent as is used in the synthesis of the abovementioned compound (I) to produce the sodium alcoholate (benzylalcoholate), then to which an equivalent mol of the compound (VI) is added, and agitated at 20° to 100° C., preferably at 50° to 90° C. for 3 to 10 hours to produce the compound (VII) in a high yield. In order to obtain the compound (IX) from the compound (VII), the compound (VII) and an equivalent mol of R¹ SH in form of its alkali or alkaline earth metal salt are dissolved in the same solvent as is used in the synthesis of the above-mentioned compound (I), preferably in aprotic polar solvents such as N,N-dimethylacetamide, dimethylformamide and dimethylsulfoxide, and stirred at 20° to 170° C., preferably at 60° to 120° C., for 3 to 10 hours to prepare the compound (IX) in a high yield. Via another route to the compound (IX), the compound (VIII) can be prepared from the compound (VI) in a high yield in a similar manner to the compound (IX) from the compound (VII) aforementioned, and also the compound (IX) from the compound (VIII) is similar to the compound (VII) from the compound (VI). In every process until the above stage, the target compound can be prepared also by utilizing the reaction of double layer system with a phase transfer catalyst in an excellent yield. The compound (X) can be obtained, for example, by treating the compound (IX) with an excess of 47% HBr under stirring at 70° to 100° C. for 3 to 7 hours. In place of HBr, hydrogen iodide (possibly in the presence of red phosphorus), trifluoroacetic acid, concentrated hydrochloric acid, magnesium iodide etherate, aluminium chloride, aluminium bromide, boron tribromide, boron trichloride or boron triiodide may be used. The compound (XI) or (XII) can be prepared from the compound (X), or from the compound (X) or (XI), respectively in a high yield in similar manner to the oxidation process of the compound (V) above.

The intermediate represented by the general formula (II)', thiazolone derivatives, can be also prepared by a well-known method from rhodanines and alkyl halides. [C.A. 75-35864K: Khim. Geterotsikl Soedin, 7(2), 189˜191 (1971)].

Examples of the pyridine, pyridazine, pyrimidine, pyrazine, isoquinoline and thiazole rings which is Ar in the general formula (I) of the present invention include ##STR7## wherein X is a halogen, Y is C₁ ˜C₄ -alkyl, C₁ ˜C₄ -alkoxy, CF₃ or nitro, Z² is hydrogen, halogen, C₁ ˜C₄ -alkyl which may be substituted by halogen, C₁ ˜C₄ -alkoxy, CF₃ or nitro, m is 0, 1, 2 or 3 in case of pyridine, or is 0, 1 or 2 in case of pyridazine, pyrimidine or pyrazine, respectively, and n and 1 are 0, 1 or 2, except that R¹ --S(O)x-- and --O--SO₂ -R² are substituted in 2- and 6-positions, R¹ is C₁ ˜C₇ -alkyl, m is 0, 1, 2 or 3 and n is zero when Ar is pyridine.

Examples of the halogen include fluorine, iodine, chlorine and bromine; examples of the C₁ ˜C₄ -alkyl include methyl, ethyl, n-propyl, isopropyl and t-butyl; examples of the C₁ ˜C₄ -alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy. Examples of the C₁ ˜C₈ -alkyl in R¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, s-pentyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, n-hexyl, 1,2,2-trimethylpropyl and n-heptyl, and those substituents may be further substituted, for example, by 1 to 3 of fluorine, chlorine or bromine and/or C₁ ˜C₄ -alkoxy and C₁ ˜C₄ -alkylthio, wherein examples of the C₁ ˜C₄ -alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl and t-butyl, and examples of the C₃ ˜C₇ -cycloalkyl or C₃ ˜C₇ -cycloalkylmethyl include cyclopropyl, cyclopropylmethyl, 2,2-dichlorocyclopropylmethyl, 2,2-dibromocyclopropylmethyl, 2,2-dichloro-1-methyl-cyclopropylmethyl, cyclobutyl, cyclobutylmethyl, 2,2,3,3-tetrafluorobutylmethyl, cyclopentyl, cyclopentylmethyl, cyclohexyl and cyclohexylmethyl. Examples of the C₁ ˜C₄ -alkyl in R² include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, chloromethyl, fluoromethyl, trifluoromethyl, bromomethyl, 2-chloroethyl, 3 -chloropropyl, 3-bromopropyl and 4-chlorobutyl.

Preferable compounds of the formula (I) in the present invention are those wherein ##STR8## X is halogen, Y² is C₁ ˜C₄ -alkyl, C₁ ˜C₄ -alkoxy, CF₃ or nitro, m and n are 0, 1, 2 or 3 provided that (m+n) is 0˜3, R¹ is C₃ ˜C₅ -alkyl which may be substituted by F or Cl, C₃ ˜C₆ -cycloalkyl or C₃ ˜C₆ -cycloalkylmethyl, R² is CH₃, CH₂ Cl or C₂ H₅, x is 0, 1 or 2.

Other preferable compounds of the formula (I) in the present invention are those wherein ##STR9## Z² is hydrogen, halogen, C₁ ˜C₄ -alkyl which may be substituted by halogen,

R¹ is C₂ ˜C₅ -alkyl which may be substituted by F or Cl, C₃ ˜C₆ -cycloalkyl or C₃ ˜C₆ -cycloalkylmethyl, allyl, R² is CH₃, CH₂ Cl or C₂ H₅ and x is 0, 1 or 2.

More preferable compounds of the formula (I) in the present invention are those wherein ##STR10## R¹ is n-C₃ H₇, iso-C₃ H₇, -sec-C₄ H ₉, -n-C₄ H₉, iso-C₄ H₉, iso-C₄ H₉, cyclopentyl or cyclopropylmethyl,

R² is CH₃, CH₂ Cl or C₂ H₅, and x is 0, 1 or 2.

Other more preferable compounds of the formula (I) in the present invention are those wherein ##STR11## Z² is hydrogen or bromine,

R¹ is C₂ H₅, n-C₃ H₇, iso-C₃ H ₇, -n-C₄ H₉, -sec-C₄ H₉, iso-C₄ H₉, --CH₂ CH₂ CH₂ Cl, --CH₂ CH₂ CH₂ F, --CH₂ CH═CH₂, cyclopentyl or cyclopropylmethyl,

R² is CH₃ or CH₂ Cl and x is 0, 1 or 2.

The most preferable compound of the formula (I) in the present invention is one selected from the group consisting of the compound of the formula: ##STR12##

The compounds of the present invention may be used alone according to the purpose of application in their practical use, but they are generally formulated by blending suitable adjuvants to improve or stabilize the effects thereof and used as such or after diluted if necessary. The compounds of the invention can be formulated in the conventional manners well-known in the art in any convenient form such as dust, granule, microgranule, wettable powder, flowable powder, emulsion, microcapsule, oil, aerosol, heating fumigant (e.g. mosquito repellent of an incense type or electric type), fuming agents such as fogging, non-heating fumigant, or toxic feed.

Examples of said adjuvants are carrier (i.e. diluent) and other adjuvants such as spreader, emulsifying agent, wetting agent, dispersing agent, fixing agent or disintegrator. Examples of the liquid carrier are aromatic hydrocarbons such as toluene or xylene; alcohols such as methanol, butanol or glycol; ketones such as acetone; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; methylnaphthalene; cyclohexane; animal or vegetable oils; fatty acids and esters thereof or the like as well as petroleum fractions such as kerosene or gas oil.

Examples of the solid carrier are clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina or saw dust.

Surfactants are generally used as an emulsifying or dispersing agent. Examples of them are anionic, cationic, non-ionic and ampholytic surfactants such as sodium salt of higher alcohol sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether or laurylbetaine.

Examples of the spreaders are polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl ether. Examples of the wetting agents are polyoxyethylene nonylphenyl ether and dialkyl sulfosuccinates. Examples of the fixing agents are carboxymethylcellulose and polyvinyl alcohol. Examples of the disintegrators are sodium ligninsulfonate and sodium laurylsulfate.

Furthermore, it is possible to blend two or more compounds of the present invention to obtain an improved insecticidal and acaricidal activities. In addition, it is also possible to use a compound of the present invention simultaneously with other physiologically active substances such as pyrethroids, e.g., allethrin, phthalthrin, permethrin, decamethrin, fenvalerate, or α-cyano-3-phenoxybenzyl- 2,2-dichloro-1-(4-ethoxyphenyl)cyclopropane-1-carboxylate and various isomers thereof, pyrethrum extract; organophosphorus pesticides, e.g., DDVP, fenitrothion, diazinon or temefos; carbamate pesticides, e.g., NAC, MTMC, BPMC or pirimor; other pesticides, acaricides or fungicides, nematicides, herbicides, plant growth regulators, fertilizers, BT, insect hormones or other pesticides, thereby affording a multipurpose composition which exhibits an improved effect and further a synergistic effect, if things go well.

It is further possible to increase the effect of the composition several times as much by adding synergists for pyrethroids such as piperonyl butoxide sulfoxide or safroxane.

Although the compounds of the present invention are stable to light, heat, and oxidation or the like, antioxidant or ultraviolet absorbers such as phenols, e.g., BHT or BHA; arylamines, e.g., α-naphthyl amine; or benzophenone compound may be added as a stabilizer to prepare a composition which exhibits a higher stability, if necessary.

The content of active ingredients in the composition of the present invention varies depending on the conditions of use such as formulation form or application method, and is usually from 0.2 to 95% by weight, preferably from 0.5 to 80% by weight, although the active ingredients may be used alone in a special case.

The composition of the present invention may be used in an amount which depends on the conditions such as formulation form, method or season for application. It is usually used in an amount of 10 to 300 g/10 a (a=100 m²), preferably 15 to 200 g/10 a in terms of the active ingredient for the agricultural and horticultural pesticide and the insecticide for forestry and pasturage, and in an amount of 2 to 200 mg/m², preferably 5 to 100 mg/m² in terms of the active ingredient for the hygienic insecticide. For example, 15 to 120 g/10 a of the active ingredient is used in the case of dust, 30 to 240 g/10 a thereof is used in the case of granule, and 40 to 250 g/10 a thereof is used the case of emulsion. However, it may be possible, or even necessary, to use the active ingredient in an amount which is outside the range as specified above, in a special case.

The insect pests on which the insecticides, acaricides and nematicides of the present invention are effective are as follows: Hemiptera such as Nephotettix cincticeps, Sogatella furcifera, Niraoarvata lugens, Laodelphax striatellus, Riptortus clavatus, Nezara viridula, Stephanis nashi, Trialeurodes vaporaviorum, Aphis gossypii, Myzus persicae and Vnaspis yanonensis; Lepidoptera such as Phyllonorycter ringoneella, Plutella xylostella, Promalactis inonisema, Adoxophyes orana, Leguminivora glycinivorella, Cnaphalocrocis medinalis, Chilo suppressalis, Ostrinia furnacalis, Mamestra brassicae, Pseudaletia separata, Spodoptera litura, Parnara guttata and Pieris rapae crucivora; Coleoptera such as Anomala cuprea, Popillia japonica, Echinocnemus soqameus, Lissorhoptrus oryzophilus, Anthonomus grandis, Oulema oryzae, Diabrotica undecimpunctata, Leptinotarsa decemlineata, Anthrenus verbasci, Tenebroides mauritanicus, Sitophilus zeamais, Henosepilachna vigintioctopunctata, Callosobruchus chinensis, Monochamus alternatus and Aulacophora femovalis; Hymenoptera such as Athalia rosae japonensis and Arge similis; Diptera such as Culex pipiens fatigans, Aedes aegypti, Asphondylia sp., Hylemya platura, Musca domesti cina, Dacus cucurbitae Agromyza oryzae; Aphaniptera such as Pulex irritans, Xenopsylla cheopis and Ctenocephalides canis; Thysanoptera such as Scirtothrips dorsalis, Thrips tabaci, Thrips palmi and Baliothrips biformis; Anoplura such as Pediculus humanus corporis and Pthirus pubis; Psocopters such as Trogium pulsatorium and Liposcelis bostrychophus; Orthoptera such as Gryllotalpa africana, Locusta migratoria, Oxya yezoensis, Blattella germanica and Periplaneta fuliginosa; and Acarina such as Tetranychus urticae, Panonychus citri, Tetranychus cinnabarinus, Tetranychus kanzawai and Rhizoglyphus echinopus.

The nematodes on which the nematicides of the present invention are effective are Tylenchida such as Heterodera glycines, Heterodera elachist, Meloidogyne incognita, Pratylenchus neglectus, Apohelenchoides besseyi, Aphelenchoides ritzemabosi and Bursa phelenchus lignicolus.

The compounds of the present invention can prevent insect pests effectively by contacting them, or control insect pests on leaves by applying the compounds at the root of plants. Thus, the compound is an excellent insecticide, acaricide or nematicide which has characteristics as a systemic insecticide with scarce phytotoxicity on the host crops.

Now, the present invention will be described by Examples.

SYNTHESIS EXAMPLE Synthesis Example 1: Synthesis of 6-isobutylthio-2-pyrazyl methanesulfonate (Compound No. 14):

(1) Synthesis of 2-benzyloxy-6-chloropyrazine as an intermediate:

7.6 g of benzylalcohol was dissolved in 65 ml of benzene, and 2.8 g of 60% sodium hydride was added little by little to the solution under stirring not so as to foam too much at room temperature. After the addition, stirring was continued for 10 min. at room temperature, followed by reflux for 1 hour. Subsequently, the solution was cooled to 50° to 60° C., and added dropwise with a solution of 10 g of 2,6-dichloropyrazine in 65 ml of benzene for 10 min. Then, after reflux for 4 hours, the reaction was finished. After cooling below 10° C., about 100 ml of water was added, and the separated benzene layer was collected. The residue obtained by distilling off the solvent was purified by silica-gel column chromatography (developing solvent: n-hexane and ethyl acetate) to obtain 12.8 g of 2-benzyloxy-6-chloropyrazine as a colourless oil (yield: 86.5%) n_(D) ²⁵ 1.5818.

(2) Synthesis of 2-benzyloxy-6-isobutylthiopyrazine as an intermediate:

12.8 g of 2-benzyloxy-6-chloropyrazine obtained by the process described in (1) and 11.2 g of potassium salt of isobutylmercaptane were dissolved in 50 ml of N,N-dimethylacetamide, followed by stirring at 70° to 80° C. for 7 hours. After cooling, the reaction mixture was poured into 500 ml of water and extracted twice by 150 ml of toluene to obtain an organic layer, which was further washed with water and then with saturated aqueous solution of common salt, followed by distilling off the solvent. The obtained residue was purified by silica-gel column chromatography (developing solvent: toluene and n-hexane) to obtain 11.1 g of 2-benzyloxy-6-isobutylthiopyrazine as a pale yellow oil (yield: 69.7%).

n_(D) ²⁵ 1.5790

PMR(CDCl₃)δ: 1.02[6H, d, -SCH₂ CH(CH₃)₂ ], 1.94 [1H, m, --SCH₂ CH(CH₃)₂ ], 3.02[2H, d, -SCH₂ CH(CH₃)₂ ], 5.40 [2H, s, --OCH₂ Ph], 7.39 [5H, s, proton in benzene ring], 7.90[1H, s, proton in pyrazine ring], 8.03[1H, s, proton in pyrazine ring] ppm.

(3) Synthesis of 2-hydroxy-6-isobutylthiopyrazine as an intermediate:

7.0 g of 2-benzyloxy-6-isobutylthiopyrazine obtained by the process described in (2) and 50 ml of acetic acid were mixed and added with 13.2 ml of 47% hydrobromic acid under stirring. The reaction was finished by stirring at 0° to 90° C. for 4 hours. The reaction mixture was cooled to room temperature and then poured into about 300 ml of chilled water. The pH of the solution was adjusted by 20% aqueous caustic soda and extracted thrice by ether. The ether layer was washed with water and then with saturated aqueous solution of common salt, followed by drying with anhydrous sodium sulfate. To the residue obtained after distilling off the solvent a small amount of the solvent mixture of toluene was added and n-hexane (1:1), was added and the mixture was filtrated to separate 4.0 g of the objective 2-hydroxy-6-isobutylpyrazine as a pale brown crystal (yield: 85.1%).

m.p. 130° to 131° C.

PMR(CDCl₃)δ: 1.05[6H, d, --SCH₂ CH(CH₃)₂ ], 1.93[1H, m, --SCH₂ CH(CH₃)₂ ], 2.97[2H, d, -SCH₂ CH(CH₃)₂ ], 7.57[1H, s, proton in pyrazine ring], 8.00[1H, s, proton in pyrazine ring], 15.50[1H, bs, ##STR13## ppm. (4) Synthesis of 6-isobutylthio-2-pyrazyl methanesulfonate (Compound No. 14) as an objective compound:

4.0 g of 2-hydroxy-6-isobutylthiopyrazine obtained by the process described in (3) and 2.4 ml of methanesulfonyl chloride were dissolved in 20 ml of N,N-dimethylacetamide and cooled to 0° to 10° C. 5.3 ml of triethylamine was added dropwise to the solution under stirring for 10 min, and then the temperature of the solution was raised gradually to room temperature, followed by stirring for 5 hours to accomplish the reaction. The reaction mixture was poured into 200 ml of water and extracted twice by ethyl acetate. The organic layer was washed with water and distilled to remove the solvent. The obtained residue was purified by silica-gel column chromatography (developer: toluene and n-hexane) to obtain 4.1 g of the objective 6-isobutylthio-2-pyrazyl methanesulfonate as a pale brown crystal (yield: 72.0%).

m.p. 65° to 66° C.

PMR(CDCl₃)δ: 1.05[6H, d, --SCH₂ CH(CH₃)₂ ], 1.98[1H, m, --SCH₂ CH(CH₃)₂ ], 3.03[2H, d, --SCH₂ CH(CH₃)₂ ], 3.46[3H, s, --OSO₂ CH₃ ], 8.08[1H, s, proton in pyrazine ring], 8.40[1H, s, proton in pyrazine ring] ppm.

Synthesis Example 2: Synthesis of 6-isobutylsulfinyl-2-pyrazyl methanesulfonate (Compound No. 15):

1.2 g of 6-isobutylthio-2-pyrazyl methanesulfonate (Compound No. 14) obtained by the process described in Synthesis Example 1 was dissolved in 10 ml of acetic acid. 1.2 ml of 30% aqueous hydrogen peroxide was added under stirring at room temperature during 30 min. After that, stirring was continued at room temperature for 3 hours and at 50° C. for further 3 hours to accomplish the reaction. The reaction mixture was cooled below room temperature and poured into 150 ml of chilled water. The organic layer obtained by extracting by methylene chloride three times was washed with water and 5% aqueous caustic soda twice, and then with water and saturated aqueous solution of common salt. The residue obtained by distilling off the solvent was purified by silica-gel column chromatography (developer: ethylacetate and n-hexane) to obtain 1.0 g of the objective 6-isobutylsulfinyl-2-pyrazyl methanesulfonate as a pale yellow oil (yield: 79.7%).

n_(D) ²⁵ 1.5308

PMR(CDCl₃)δ: 1.11, 1.21[6H, d, d, --SOCH₂ CH(CH₃)₂ ], 2.36, 2.43[1H, m, m, --SOCH₂ CH(CH₃)], 2.92, 2.95 [2H, d, d, --SOCH₂ CH(CH₃)₂ ], 3.51[3H, s, -OSO₂ CH₃ ], 8.63[1H, s, proton in pyrazine ring], 9.15[1H, s, proton in pyrazine ring] ppm.

Synthesis Example 3: Synthesis of 4-isobutylthio-2-pyridyl methanesulfonate (Compound No. 30):

1.3 g of 4-isobutylthio-2-pyridone (m.p. 119 to 120° C.) and 0.7 ml of methanesulfonyl chloride were dissolved in 10 ml of methylene chloride, and cooled below 10° C. 1.5 ml of triethylamine was added dropwise to the solution with stirring. By stirring at room temperature for 4 hours, the reaction was completed. The reaction solution was poured into 100 ml of water, followed by addition of 100 ml of methylene chloride for separation. The methylene chloride layer was washed with water and saturated aqueous solution of common salt, then distilled to remove the solvent. The obtained residue was purified by silica-gel column chromatography (developer: benzene and n-hexane) to obtain 1.7 g of the objective 4-isobutylthio-2-pyridyl methanesulfonate (yield: 91.6%) as a colourless oil, which were allowed to stand to crystallization.

m.p. 34° to 35° C.

PMR(CDCl₃)δ: 1.06[6H, d, --SCH₂ CH(CH₃)₂ ], 1.97[1H, m, --SCH₂ CH(CH₃)₂ ], 2.86[2H, d, --SCH₂ CH(CH₃)₂ ], 3.49[3H, s, --OSO₂ CH₃ ], 6.88[1H, d, proton in pyridine ring], 7.06[1H, d-d, proton in pyridine ring], 8.08[1H, d, proton in pyridine ring] ppm.

Synthesis Example 4: Synthesis of 4-isobutylsulfonyl-2-pyridyl methanesulfonate (Compound No. 32):

1.7 g of 4-isobutylthio-2-pyridyl methanesulfonate (Compound No. 30) obtained by the process described in Synthesis Example 3 was dissolved in 10 ml of acetic acid, followed by adding 1.5 ml of 30% aqueous hydrogen peroxide below 10° C. and stirring at room temperature for 2 hours. Further, 0.5 ml of 30% aqueous hydrogen peroxide was added to the reaction mixture, which was stirred at 40° C. for 8 hours to accomplish the reaction. After cooling, the reaction solution was poured into 100 ml of chilled water and extracted three times with 100 ml of methylene chloride. The organic layer was washed twice with 5% aqueous caustic soda, then with water and saturated aqueous solution of common salt, followed by distilling off the solvent. The obtained residue was purified by silica-gel column chromatography (developer: ethyl acetate and n-hexane) to obtain 1.3 g of the objective 4-isobutylsulfonyl-2-pyridyl methanesulfonate as a colourless crystal (yield: 68.2%).

m.p. 75.5° to 76.5° C.

PMR(CDCl₃)δ: 1.10[6H, d, --SCH₂ CH(CH₃)₂ ], 2.29[1H, m, --SCH₂ CH(CH₃)₂ ], 3.06[2H, d, --SCH₂ CH(CH₃)₂ ], 3.55[3H, s, --OSO₂ CH₃ ], 7.59[1H, d, proton in pyridine ring], 7.76[1H, d-d, proton in pyridine ring], 8.65[1H, d, proton in pyridine ring] ppm.

Synthesis Example 5: Synthesis of 5-isobutylthio-3-pyridyl trifluoromethylsulfonate (Compound No. 45):

A mixture of 0.5 g of 5-isobutylthio-3-pyridinol (m.p. 83° to 84° C.) and 0.5 ml of pyridine was cooled to 5° to 10° C. 1 g of trifluoromethanesulfonic anhydride was added with stirring to the mixture, which was stirred at this temperature for 30 min. The reaction was continued at room temperature for further 5 hours. The reaction solution was poured into 100 ml of chilled water and extracted twice by 50 ml of toluene. The toluene layer obtained was washed twice by water. The residue obtained by distilling off the solvent was purified by silica-gel column chromatography (developer: ethylacetate and n-hexane) to obtain 0.9 g of the objective 5-isobutylthio-3-pyridyl trifluoromethanesulfonate as a colourless oil (yield: 95.1%).

n_(D) ²⁵ 1.4875

PMR(CDCl₃)δ: 1.07[6H, d, --SCH₂ CH(CH₃)₂ ], 1.91[1H, m, --SCH₂ CH(CH₃)₂ ], 2.87[2H, d, --SCH₂ CH(CH₃)₂ ], 7.49[1H, t, proton in pyridine ring], 8.33[1H, d, proton in pyridine ring], 8.53[1H, d, proton in pyridine ring] ppm.

Other compounds of the present invention were synthesized according to the same procedure as the ones described in Synthesis Examples 1 to 5. Typical compounds among the obtained ones shown in Table 1.

                                      TABLE 1                                      __________________________________________________________________________     R.sup.1S(O)x[Ar]OSO.sub.2R.sup.2                             (I)               Compound No.                                                                           formula                    m.p. or b.p. (refractive                                                                        appearance                 __________________________________________________________________________              ##STR14##                 (n.sub.D.sup.25 1.5620)                                                                         colourless oil             2                                                                                       ##STR15##                 (n.sub.D.sup.25 1.5370)                                                                         "                          3                                                                                       ##STR16##                 (n.sub.D.sup.25 1.5635)                                                                         pale yellow oil            4                                                                                       ##STR17##                 (n.sub.D.sup.25 1.5569)                                                                         "                          5                                                                                       ##STR18##                 mp 71-72° C.                                                                             colourless crystal         6                                                                                       ##STR19##                 mp 116-117° C.                                                                           "                          7                                                                                       ##STR20##                 mp 61-63° C.                                                                             "                          8                                                                                       ##STR21##                 (n.sub.D.sup.25 1.5242)                                                                         colourless oil             9                                                                                       ##STR22##                 (n.sub.D.sup.25 1.5365)                                                                         "                          10                                                                                      ##STR23##                 (n.sub.D.sup.25 1.5409)                                                                         colourless oil             11                                                                                      ##STR24##                 (n.sub.D.sup.25 1.5331)                                                                         "                          12                                                                                      ##STR25##                 bp 146-154° C./0.6-0.65                                                                  "mHg                       13                                                                                      ##STR26##                 mp 86-87° C.                                                                             pale yellow crystal        14                                                                                      ##STR27##                 mp 65-66° C.                                                                             brown crystal              15                                                                                      ##STR28##                 (n.sub.D.sup.25 1.5308)                                                                         pale yellow oil            16                                                                                      ##STR29##                 (n.sub.D.sup.25 1.5183)                                                                         "                          17                                                                                      ##STR30##                 mp 98-99° C.                                                                             pale yellow crystal        18                                                                                      ##STR31##                 mp 120-121° C.                                                                           colourless crystal         19                                                                                      ##STR32##                 mp 64-66° C.                                                                             "                          20                                                                                      ##STR33##                 mp 100-101° C.                                                                           "                          21                                                                                      ##STR34##                 mp 106-107° C.                                                                           "                          22                                                                                      ##STR35##                 mp 116-117° C.                                                                           pale yellow crystal        23                                                                                      ##STR36##                 mp 56.5-57.5° C.                                                                         colourless crystal         24                                                                                      ##STR37##                 (n.sub.D.sup.25 1.5285)                                                                         colourless oil             25                                                                                      ##STR38##                 mp 79.5-80° C.                                                                           colourless crystal         26                                                                                      ##STR39##                 mp 88-89° C.                                                                             yellow crystal             27                                                                                      ##STR40##                 mp 99-100° C.                                                                            "                          28                                                                                      ##STR41##                 mp 114-115° C.                                                                           pale yellow crystal        29                                                                                      ##STR42##                 mp 46-47° C.                                                                             colourless crystal         30                                                                                      ##STR43##                 mp 34-35° C.                                                                             "                          31                                                                                      ##STR44##                 mp 79-80° C.                                                                             colourless crystal         32                                                                                      ##STR45##                 mp 75.5-76.5° C.                                                                         "                          33                                                                                      ##STR46##                 (n.sub.D.sup.25 1.5371)                                                                         pale yellow oil            34                                                                                      ##STR47##                 (n.sub.D.sup.25 1.5440)                                                                         "                          35                                                                                      ##STR48##                 (n.sub.D.sup.25 1.5229)                                                                         "                          36                                                                                      ##STR49##                 (n.sub.D.sup.25 1.5470)                                                                         yellow oil                 37                                                                                      ##STR50##                 mp 87-88° C.                                                                             colourless crystal         38                                                                                      ##STR51##                 (n.sub.D.sup.25 1.5434)                                                                         colourless oil             39                                                                                      ##STR52##                 mp 65-67° C.                                                                             colourless crystal         40                                                                                      ##STR53##                 mp 67-68° C.                                                                             "                          41                                                                                      ##STR54##                 (n.sub.D.sup.25 1.5390)                                                                         pale yellow oil            42                                                                                      ##STR55##                 mp 96-97° C.                                                                             colourless crystal         43                                                                                      ##STR56##                 mp 110-111° C.                                                                           "                          44                                                                                      ##STR57##                 mp 38 -40° C.                                                                            "                          45                                                                                      ##STR58##                 (n.sub.D.sup.25 1.4875)                                                                         colourless oil             46                                                                                      ##STR59##                 (n.sub.D.sup.25 1.5511)                                                                         "                          47                                                                                      ##STR60##                 (n.sub.D.sup.25 1.5434)                                                                         colourless oil             48                                                                                      ##STR61##                 mp 56-57° C.                                                                             colourless crystal         49                                                                                      ##STR62##                 mp 79-80° C.                                                                             "                          50                                                                                      ##STR63##                 mp 86.5-87° C.                                                                           "                          51                                                                                      ##STR64##                 mp 74-75° C.                                                                             "                          52                                                                                      ##STR65##                                                             53                                                                                      ##STR66##                                                             54                                                                                      ##STR67##                                                             55                                                                                      ##STR68##                                                             56                                                                                      ##STR69##                                                             57                                                                                      ##STR70##                                                             58                                                                                      ##STR71##                                                             59                                                                                      ##STR72##                                                             60                                                                                      ##STR73##                                                             61                                                                                      ##STR74##                                                             62                                                                                      ##STR75##                                                             63                                                                                      ##STR76##                                                             64                                                                                      ##STR77##                                                             65                                                                                      ##STR78##                                                             66                                                                                      ##STR79##                                                             67                                                                                      ##STR80##                                                             68                                                                                      ##STR81##                                                             69                                                                                      ##STR82##                                                             70                                                                                      ##STR83##                                                             71                                                                                      ##STR84##                                                             72                                                                                      ##STR85##                                                             73                                                                                      ##STR86##                                                             74                                                                                      ##STR87##                                                             75                                                                                      ##STR88##                                                             76                                                                                      ##STR89##                                                             77                                                                                      ##STR90##                                                             78                                                                                      ##STR91##                                                             79                                                                                      ##STR92##                                                             80                                                                                      ##STR93##                                                             81                                                                                      ##STR94##                                                             82                                                                                      ##STR95##                                                             83                                                                                      ##STR96##                                                             84                                                                                      ##STR97##                                                             85                                                                                      ##STR98##                                                             86                                                                                      ##STR99##                                                             87                                                                                      ##STR100##                                                            88                                                                                      ##STR101##                                                            89                                                                                      ##STR102##                                                            90                                                                                      ##STR103##                                                            91                                                                                      ##STR104##                                                            92                                                                                      ##STR105##                                                            93                                                                                      ##STR106##                                                            94                                                                                      ##STR107##                (n.sub.D.sup.25 1.5507)                                                                         colourless oil             95                                                                                      ##STR108##                (n.sub.D.sup.25 1.5481)                                                                         "                          96                                                                                      ##STR109##                m.p. 71-72° C.                                                                           colourless crystal         97                                                                                      ##STR110##                (n.sub.D.sup.25 1.5361)                                                                         pale yellow oil            98                                                                                      ##STR111##                                                            99                                                                                      ##STR112##                                                            100                                                                                     ##STR113##                                                            101                                                                                     ##STR114##                                                            102                                                                                     ##STR115##                                                            103                                                                                     ##STR116##                                                            104                                                                                     ##STR117##                                                            105                                                                                     ##STR118##                                                            106                                                                                     ##STR119##                                                            107                                                                                     ##STR120##                                                            108                                                                                     ##STR121##                                                            109                                                                                     ##STR122##                                                            110                                                                                     ##STR123##                                                            111                                                                                     ##STR124##                                                            112                                                                                     ##STR125##                                                            113                                                                                     ##STR126##                                                            114                                                                                     ##STR127##                                                            115                                                                                     ##STR128##                                                            116                                                                                     ##STR129##                                                            117                                                                                     ##STR130##                                                            118                                                                                     ##STR131##                                                            119                                                                                     ##STR132##                                                            120                                                                                     ##STR133##                                                            121                                                                                     ##STR134##                                                            122                                                                                     ##STR135##                                                            123                                                                                     ##STR136##                                                            124                                                                                     ##STR137##                                                            125                                                                                     ##STR138##                                                            126                                                                                     ##STR139##                                                            127                                                                                     ##STR140##                                                            128                                                                                     ##STR141##                                                            129                                                                                     ##STR142##                                                            130                                                                                     ##STR143##                                                            131                                                                                     ##STR144##                                                            132                                                                                     ##STR145##                                                            133                                                                                     ##STR146##                                                            134                                                                                     ##STR147##                                                            135                                                                                     ##STR148##                                                            136                                                                                     ##STR149##                (n.sub.D.sup.25 1.6028)                                                                         colourless oil             137                                                                                     ##STR150##                                                            138                                                                                     ##STR151##                                                            139                                                                                     ##STR152##                                                            140                                                                                     ##STR153##                (n.sub.D.sup.25 1.5152)                                                                         colourless oil             141                                                                                     ##STR154##                (n.sub.D.sup.25 1.5554)                                                                         "                          142                                                                                     ##STR155##                                                            143                                                                                     ##STR156##                mp 81-82° C.                                                                             colourless crystal         144                                                                                     ##STR157##                                                            145                                                                                     ##STR158##                                                            146                                                                                     ##STR159##                                                            147                                                                                     ##STR160##                                                            148                                                                                     ##STR161##                                                            149                                                                                     ##STR162##                                                            150                                                                                     ##STR163##                (n.sub.D.sup.25 1.5402)                                                                         colourless oil             151                                                                                     ##STR164##                                                            152                                                                                     ##STR165##                (n.sub.D.sup.25 1.5144)                                                                         colourless oil             153                                                                                     ##STR166##                                                            154                                                                                     ##STR167##                                                            155                                                                                     ##STR168##                                                            156                                                                                     ##STR169##                mp 47-48° C.                                                                             colourless crystal         157                                                                                     ##STR170##                (n.sub.D.sup.25 1.5322)                                                                         colourless oil             158                                                                                     ##STR171##                mp 59.5-60.5° C.                                                                         colourless crystal         159                                                                                     ##STR172##                mp 116-117° C.                                                                           colourless crystal         160                                                                                     ##STR173##                (n.sub.D.sup.25 1.5325)                                                                         pale yellow oil            161                                                                                     ##STR174##                mp 54-55° C.                                                                             colourless crystal         162                                                                                     ##STR175##                mp 63-65° C.                                                                             "                          163                                                                                     ##STR176##                (n.sub.D.sup.25 1.5597)                                                                         colourless                 __________________________________________________________________________                                                         oil                   

Synthesis Example 6: Preparation of 2-n- 4-methylsulfonyloxy-1,3-thiazole (No. 164)

8 g of 2-n-propylthio-1,3-thiazoline-4-one and 4.8 g of anhydrous sodium carbonate were suspended in acetonitrile, followed by stirring. 7.9 g of methanesulfonyl chloride was added dropwise to the suspension below 10° C. After the addition, the reaction was continued under stirring at room temperature for 2 hours. The reaction solution was poured into water and extracted by ether. The ether layer was washed with a saturated aqueous solution of common salt and dried over anhydrous sodium sulfate. The oil obtained by concentration was purified by silica-gel column chromatography by 9.1 g of the objective compound as a yellow oil (yield: 78.8%)

n_(D) ²⁵ 1.5510

PMR(CDCl₃)δ: 1.05 (t, 3H), 1.78 (m, 2H), 3.12 (t, 2H), 3.32 (s, 3H), 6.76 (s, 1H) ppm.

Synthesis Example 7: Preparation of 2-isopropylthio-4-methylsulfonyloxy-1,3-thiazole (No. 171):

8 g of 2-isopropylthio-1,3-thiazoline-4-one was dissolved in 100 ml of methylene chloride and cooled below 10° C. Then, 7.8 g of methanesulfonyl chloride and 12.6 ml of triethylamine were added dropwise to the solution below 15° C. with attention to out-break of heat. After that, the reaction was continued with stirring at room temperature for 2 hours. Water was added to the reaction mixture and extracted by ether. The ether layer was washed with water and dried over anhydrous sodium sulfate. The oil obtained by concentration was purified by silica-gel column chromatography to obtain 9.1 g of the objective compound as a pale brown crystal (yield: 78.8%).

m.p. 83° to 85° C.

PMR(CDCl₃) δ: 1.47 (d, 6H), 3.38 (s, 3H), 3.60˜3.90 (m, 1H), 6.94 (s, 1H) ppm.

Synthesis Example 8: Preparation of 2-isopropylsulfonyl-4-methylsulfonyloxy-1,3-thiazole (No. 176):

2.5 g of 2-isopropylthio-4-methylsulfonyloxy-1,3-thiazole was dissolved in 10 ml of acetic acid. 2.9 ml of 35% aqueous hydrogen peroxide was added to the solution and the reaction was continued at 70° to 80° C. for 2 hours. The reaction mixture was poured into cold water and neutralized with 5% aqueous sodium hydroxide. The neutral solution was extracted by ethyl acetate and washed with saturated aqueous solution of common salt, followed by drying over anhydrous sodium sulfate to be concentrated to 2.5 g of a white crystal of the objective compound (yield: 88.7%).

m.p. 56.5° to 58.5° C.

PMR (CDCl₃) δ: 1.48 (d, 6H), 3.48 (s, 3H), 3.48˜3.80 (m, 1H), 7.66 (s, 1H) ppm.

Synthesis Example 9: Preparation of 2-sec-butylsulfinyl-4-methylsulfonyloxy-1,3-thiazole (No. 203):

4.0 g of 2-sec-butylthio-4-methylsulfonyloxy-1,3-thiazole was dissolved in 15 ml of acetic acid, and 2.2 ml of 35% aqueous hydrogen peroxide was added to the solution at room temperature, followed by reaction at 30° to 40° C. for 4 hours. The reaction mixture was poured into chilled water, neutralized by 5% aqueous solution of sodium hydroxide, and extracted with ethyl acetate. The extract was washed with a saturated aqueous solution of common salt, dried over anhydrous sodium sulfate and concentrated to obtain an oil, which was purified by silica-gel column chromatography to 2.1 g of the objective compound as a pale yellow oil (yield: 49.7%).

n_(D) ²⁵ 1.5421

PMR(CDCl₃) δ: 1.04 to 1.56 (m, 6H), 1.56 to 2.44 (m, 2H), 3.08 to 3.48 (m, 1H), 3.66(s, 3H), 8.07 (s, 1H) ppm.

Synthesis Example 10: Preparation of 2-(3-fluoropropylthio)-4-methylsulfonyloxy-1,3-thiazole (No. 206):

6.2 g of 2-(3-fluoropropylthio)-1,3-thiazoline-4-one was dissolved in 80 ml of methylene chloride and cooled below 10° C. 5.5 g of methanesulfonyl chloride and 8.9 ml of triethylamine were added dropwise to the solution keeping the temperature below 15° C., followed by stirring at room temperature for 2 hours. After addition of water, the reaction mixture was extracted by methylene chloride, then organic layer is washed with water and dried over anhydrous sodium sulfate, followed by concentration to an oil, which is purified by silica-gel column chromatography to obtain 6.0 g of the objective compound as a pale brown oil (yield: 69.1%).

n_(D) ²⁵ 1.5389

PMR(CDCl₃) δ: 1.90 to 2.20 (m, 2H), 3.16 to 3.40 (m, 2H), 3.28 (s, 3H), 4.24 (t, 1H), 4.70 (t, 1H), 6.74 (s, 1H) ppm.

Synthesis Example 11: Preparation of 2-isopropylthio-4-methylsulfonyloxy-5-chloro-1,3-thiazole (No. 230):

3.5 g of 2-isopropylthio-4-methylsulfonyloxy-1,3-thiazole (No. 171) was dissolved in 50 ml of methylene chloride. 2 g of sulfuryl chloride was added dropwise to the solution keeping the temperature below 0° C., followed by stirring at room temperature for 2 hours. Then, 20% aqueous solution of sodium carbonate was added to the reaction mixture to cease the reaction, and the methylene chloride layer was separated and washed with water, followed by drying over anhydrous sodium sulfate. The oil obtained by concentration was purified by silica-gel column chromatography to 2 g of the objective compound as a pale yellow oil (yield; 50.4%).

n_(D) ²⁵ 5587

PMR(CDCl₃) δ: 1.45 (d, 6H), 3.46 (s, 3H), 3.60 to 4.00 (m, 1H) ppm.

Synthesis Example 12: Preparation of 2-isopropylthio-4-methylsulfonyloxy-5-bromo-1,3-thiazole (No. 233):

3.5 g of 2-isopropylthio-4-methylsulfonyloxy-1,3-thiazole was dissolved in 50 ml of ether, and 0.8 ml of bromine was added dropwise to the solution keeping the temperature below 0° C. After the addition, the solution was stirred at room temperature for 2 hours, then 5% solution of sodium hydrogen sulfite was added thereto to separate ether layer, which was washed with water and dried over anhydrous sodium sulfate, followed by concentration to an oil. The oil was purified by silica-gel column chromatography to obtain 3.7 g of the objective compound as a yellow oil (yield: 80.7%).

n_(D) ²⁵ 1.5763

PMR(CDCl₃) δ: 1.45 (d, 6H), 3.45 (s, 3H), 3.60 to 4.00 (m, 1H) ppm.

Other compounds of the present invention were synthesized according to the same procedures as the ones described in Synthesis Examples 6 to 12. Typical compounds among the obtained ones shown in Table 2.

                                      TABLE 2                                      __________________________________________________________________________      ##STR177##                                                                    Compound                        yield                                          No.   R.sup.1        x R.sup.2                                                                              R.sup.3                                                                           (%)                                                                               n.sub.D.sup.25 (mp °C.)                                                         appearance                          __________________________________________________________________________     164   CH.sub.3 CH.sub.2 CH.sub.2                                                                    0 CH.sub.3                                                                             H  78.8                                                                              1.5510  yellow oil                          165   CH.sub.3 CH.sub.2 CH.sub.2                                                                    1 CH.sub.3                                                                             H  65.9                                                                              1.5462  pale yellow oil                     166   CH.sub.3 CH.sub.2 CH.sub.2                                                                    2 CH.sub.3                                                                             H  88.7                                                                              (83-85° C.)                                                                     colourless crystal                  167   CH.sub.3       0 CH.sub.3                                                                             H  74.6                                                                              1.5616  brown oil                           168   CH.sub.3       2 CH.sub.3                                                                             H  73.5                                                                              (97-98.5° C.)                                                                   colourless crystal                  169   CH.sub.3 CH.sub.2                                                                             0 CH.sub.3                                                                             H  66.5                                                                              1.5594  pale brown oil                      170   CH.sub.2CHCH.sub.2                                                                            0 CH.sub.3                                                                             H  77.9                                                                              1.5669  pale brown oil                      171                                                                                   ##STR178##    0 CH.sub.3                                                                             H  78.8                                                                              (83-85° C.)                                                                     pale brown crystal                  172   CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2                                                           0 CH.sub.3                                                                             H  86.7                                                                              1.5450  pale brown oil                      173                                                                                   ##STR179##    0 CH.sub.3                                                                             H  79.7                                                                              1.5440  pale brown oil                      174                                                                                   ##STR180##    2 CH.sub.3                                                                             H  96.8                                                                              (58-60° C.)                                                                     colourless crystal                  175   CH.sub.3 CH.sub.2                                                                             2 CH.sub.3                                                                             H  79.4                                                                              (57.5-59° C.)                                                                   colourless crystal                  176                                                                                   ##STR181##    2 CH.sub.3                                                                             H  88.7                                                                              (56.5-58.5° C.)                                                                 colourless crystal                  177   CH.sub.2CHCH.sub.2                                                                            2 CH.sub.3                                                                             H  11.8                                                                              (77-79° C.)                                                                     colourless crystal                  178   CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2                                                           2 CH.sub.3                                                                             H  85.7                                                                              (75.5-76.5° C.)                                                                 colourless crystal                  179   CH.sub.3       1 CH.sub.3                                                                             H  56.1                                                                              (71.5-73.5° C.)                                                                 colourless crystal                  180   CH.sub.3 CH.sub.2                                                                             1 CH.sub.3                                                                             H  49.8                                                                              (63-65° C.)                                                                     colourless crystal                  181   CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2                                                           1 CH.sub.3                                                                             H  77.8                                                                              (48-49.5° C.)                                                                   colourless crystal                  182                                                                                   ##STR182##    1 CH.sub.3                                                                             H  76.7                                                                              (46-48° C.)                                                                     colourless crystal                  183                                                                                   ##STR183##    0 CH.sub.3                                                                             H  70.6                                                                              1.5392  pale brown oil                      184   CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                         0 CH.sub.3                                                                             H  79.7                                                                              1.5330  pale brown oil                      185   ClCH.sub.2 CH.sub.2 CH.sub.2                                                                  0 CH.sub.3                                                                             H  53.8                                                                              1.5662  pale brown oil                      186   ClCH.sub.2 CH.sub.2 CH.sub.2                                                                  0 CH.sub.2 CH.sub.3                                                                    H  43.3                                                                              1.5558  pale brown oil                      187   CH.sub.3 CH.sub.2 CH.sub.2                                                                    0 CH.sub.2 CH.sub.3                                                                    H  46.6                                                                              1.5452  pale brown oil                      188   CHCCH.sub.2    0 CH.sub.3                                                                             H  77.3                                                                              1.5740  pale brown oil                      189                                                                                   ##STR184##    0 CH.sub.3                                                                             H  73.4                                                                              (41-43° C.)                                                                     pale yellow crystal                 190   CH.sub. 3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                 0 CH.sub.3                                                                             H  73.5                                                                              (44.5-45.5° C.)                                                                 pale yellow crystal                 191                                                                                   ##STR185##    0 CH.sub.3                                                                             H  76.3                                                                              1.5388  pale brown oil                      192   CH.sub.2CHCH.sub.2                                                                            1 CH.sub.3                                                                             H  35.2                                                                              (66-68° C.)                                                                     pale yellow crystal                 193                                                                                   ##STR186##    1 CH.sub.3                                                                             H  79.9                                                                              (31.5-33° C.)                                                                   colourless crystal                  194   ClCH.sub.2 CH.sub.2 CH.sub.2                                                                  2 CH.sub.3                                                                             H  89.9                                                                              (92-94° C.)                                                                     colourless crystal                  195   ClCH.sub.2 CH.sub.2 CH.sub.2                                                                  2 CH.sub.2 CH.sub.3                                                                    H  72.6                                                                              1.5312  colourless oil                      196   CH.sub.3 CH.sub.2 CH.sub.2                                                                    2 CH.sub.2 CH.sub.3                                                                    H  96.2                                                                              1.5225  colourless oil                      197                                                                                   ##STR187##    2 CH.sub.3                                                                             H  89.8                                                                              (40.5-41.5° C.)                                                                 colourless crystal                  198   CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                         2 CH.sub.3                                                                             H  87.6                                                                              (60-62° C.)                                                                     colourless crystal                  199                                                                                   ##STR188##    2 CH.sub.3                                                                             H  71.5                                                                              1.5230  colourless oil                      200   CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                  2 CH.sub.3                                                                             H  89.7                                                                              (73-74.5° C.)                                                                   colourless crystal                  201                                                                                   ##STR189##    2 CH.sub.3                                                                             H  63.8                                                                              1.5185  colourless oil                      202   ClCH.sub.2 CH.sub.2 CH.sub.2                                                                  1 CH.sub.3                                                                             H  66.9                                                                              1.5633  colourless oil                      203                                                                                   ##STR190##    1 CH.sub.3                                                                             H  49.7                                                                              1.5421  pale yellow oil                     204                                                                                   ##STR191##    1 CH.sub.3                                                                             H  84.1                                                                              1.5324  pale yellow oil                     205                                                                                   ##STR192##    0 CH.sub.2 CH.sub.3                                                                    H  49.9                                                                              1.5381  pale brown oil                      206   FCH.sub.2 CH.sub.2 CH.sub.2                                                                   0 CH.sub.3                                                                             H  69.1                                                                              1.5389  pale brown oil                      207   FCH.sub.2 CH.sub.2 CH.sub.2                                                                   2 CH.sub.3                                                                             H  82.6                                                                              (88-89.5° C.)                                                                   colourless crystal                  208   FCH.sub.2 CH.sub.2 CH.sub.2                                                                   0 CH.sub.2 CH.sub.3                                                                    H  41.3                                                                              1.5307  pale yellow oil                     209                                                                                   ##STR193##    0 CH.sub.3                                                                             H  57.0                                                                              1.6007  pale brown oil                      210                                                                                   ##STR194##    2 CH.sub.3                                                                             H  81.4                                                                              (122-123° C.)                                                                   colourless crystal                  211                                                                                   ##STR195##    0 CH.sub.3                                                                             CH.sub.3                                                                          61.3                                                                              (39.5-41° C.)                                                                   pale yellow crystal                 212                                                                                   ##STR196##    1 CH.sub.3                                                                             CH.sub.3                                                                          70.8                                                                              1.5329  colourless oil                      213                                                                                   ##STR197##    2 CH.sub.3                                                                             CH.sub.3                                                                          77.4                                                                              (70-71.5° C.)                                                                   colourless crystal                  214                                                                                   ##STR198##    0 CH.sub.3                                                                             H  75.6                                                                              (41-42.5° C.)                                                                   pale brown crystal                  215                                                                                   ##STR199##    1 CH.sub.3                                                                             H  35.5                                                                              1.5572  pale yellow oil                     216                                                                                   ##STR200##    2 CH.sub.3                                                                             H  84.0                                                                              (104- 105° C.)                                                                  colourless crystal                  217                                                                                   ##STR201##    0 CH.sub.3                                                                             Cl 56.1                                                                              1.5501  pale brown oil                      218                                                                                   ##STR202##    1 CH.sub.3                                                                             Cl 63.3                                                                              (85.5-87.5° C.)                                                                 colourless crystal                  219                                                                                   ##STR203##    2 CH.sub.3                                                                             Cl 90.4                                                                              (68-69.5° C.)                                                                   colourless crystal                  220                                                                                   ##STR204##    0 CH.sub.3                                                                             Br 73.8                                                                              1.5709  pale brown oil                      221                                                                                   ##STR205##    2 CH.sub.3                                                                             Br 87.0                                                                              (74-75.5° C.)                                                                   colourless crystal                  222                                                                                   ##STR206##    0 CH.sub.3                                                                             *.sup.1                                                                           36.5                                                                              1.5284  pale yellow oil                     223                                                                                   ##STR207##    2 CH.sub.3                                                                             *.sup.2                                                                           90.6                                                                              1.5129  colourless oil                      224                                                                                   ##STR208##    0 *.sup.3                                                                              H  51.5                                                                              1.5302  pale brown oil                      225                                                                                   ##STR209##    0 *.sup.4                                                                              H  70.4                                                                              1.5450  pale brown oil                      226                                                                                   ##STR210##    2 *.sup.5                                                                              H  79.4                                                                              1.5322  colourless oil                      227                                                                                   ##STR211##    0 *.sup.6                                                                              H  52.4                                                                              1.5482  pale brown oil                      228                                                                                   ##STR212##    0 CH.sub.3                                                                             H  66.2                                                                              1.5290  pale brown oil                      229                                                                                   ##STR213##    2 CH.sub.3                                                                             H  94.5                                                                              1.5090  colourless oil                      230                                                                                   ##STR214##    0 CH.sub.3                                                                             Cl 50.4                                                                              1.5587  pale yellow oil                     231   ClCH.sub.2 CH.sub.2 CH.sub.2                                                                  0 CH.sub.3                                                                             Cl 48.5                                                                              1.5780  pale brown oil                      232                                                                                   ##STR215##    0 CH.sub.3                                                                             Cl 43.3                                                                              (35-37° C.)                                                                     pale brown crystal                  233                                                                                   ##STR216##    0 CH.sub.3                                                                             Br 80.7                                                                              1.5763  yellow oil                          234   ClCH.sub.2 CH.sub.2 CH.sub.2                                                                  0 CH.sub.3                                                                             Br 67.3                                                                              (44-46° C.)                                                                     pale brown crystal                  235                                                                                   ##STR217##    0 CH.sub.3                                                                             Br 55.8                                                                              (44-46° C.)                                                                     brown crystal                       236                                                                                   ##STR218##    0 CH.sub.3                                                                             H  76.5                                                                              1.5655  pale brown oil                      237                                                                                   ##STR219##    1 CH.sub.3                                                                             H  78.6                                                                              (78.5-80.5° C.)                                                                 colourless crystal                  238                                                                                   ##STR220##    2 CH.sub.3                                                                             H  72.3                                                                              1.5417  colourless oil                      239                                                                                   ##STR221##    0 CH.sub.3                                                                             H  64.1                                                                              (70-72° C.)                                                                     pale yellow crystal                 240                                                                                   ##STR222##    1 CH.sub.3                                                                             H  76.7                                                                              (59-61° C.)                                                                     colourless crystal                  241                                                                                   ##STR223##    2 CH.sub.3                                                                             H  78.5                                                                              1.5335  colourless oil                      __________________________________________________________________________      Note:                                                                          *.sup.1 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                    *.sup.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3,                                   *.sup.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3,                                   *.sup.4 CH.sub. 2 CH.sub.2 CH.sub.2 Cl                                         *.sup.5 CH.sub.2 CH.sub.2 CH.sub.2 Cl,                                         *.sup.6 CH.sub.2 CH.sub.2 CH.sub.3                                       

FORMULATION EXAMPLE Formulation Example 1: Emulsifiable concentration

20 parts of a compound of the present invention was dissolved in 65 parts of a xylene/methylnaphthalene mixture. 15 parts of a mixture of an alkylphenol/ethylene oxide condensate and calcium alkylbenzenesulfonate in a ratio of 8:2 was mixed with the obtained solution to prepare at emulsifiable concentration. This emulsifiable concentration may be used as a spreading agent by diluting with water.

Formulation Example 2: Wettable powder

20 parts of a compound of the present invention was mixed with 35 parts of kaolin, 30 parts of clay and 7.5 parts of diatomaceous earth. 7.5 parts of a mixture of sodium laurate and sodium dinaphthylmethanesulfonate in a ratio of 1:1 was added to the obtained mixture. The resulting mixture was finely ground to prepare a powder. This powder may be used as a spreading agent by diluting with water.

Formulation Example 3: Dust

1 part of a compound of the present invention was mixed with 97 parts of a mixture of talc and calcium carbonate in a ratio 1:1. The resulting mixture was ground to prepare a homogeneously dispersed mixture. 2 parts of silicic acid anhydride was added to this mixture. The resulting mixture was mixed and ground to prepare a dust. This dust may be used as a spreading agent as such.

Formulation Example 4: Granule

2 parts of a compound of the present invention was mixed with 48 parts of finely powdered bentonite, 48 parts of talc and 2 parts of sodium ligninsulfonate, followed by the addition of water. The resulting mixture was kneaded until it became homogeneous. The mixture was granulated by passing it through an injection molding machine and adjusted to a granular size of 0.1 to 1 mm by passing the granule thus molded through a spherizer, a dryer and sieve. The obtained granule may be directly spreaded on the surface of paddy fields and uplands as such.

Formulation Example 5: Oil

A mixture of 0.1 part of a compound of the present invention and 0.5 part of piperonyl butoxide was dissolved in such amount of illuminating kerosene as to give the total volume of 100 parts to prepare an oil. This oil may be used as such.

Formulation Example 6: Aerosol

0.4 part of a compound of the present invention, 20 parts of piperonyl butoxide, 6 parts of xylene and 7.6 parts of deodorized kerosine were mixed and dissolved. After filling the mixture into an aerosol container, a valve was fitted. 86 parts of Freon was introduced into the container through the valve under pressure to obtain an aerosol.

Formulation Example 7: Heating fibrous fumigant insecticidal composition

0.05 g of a compound of the present invention was dissolved in an appropriate amount of chloroform. The obtained solution was homogeneously adsorbed on the surface of an asbestos (2.5×1.5 mm, 0.3 mm in thickness) to prepare a fibrous fumigant insecticidal composition of hot plate heating type.

Formulation Example 8: Mosquito-repellant incense

0.5 g of a compound of the present invention was dissolved in 20 ml of methanol, followed by the addition of 99.5 g of an incense carrier comprising tabu powder, pyrethrum marc and wood powder in a ratio of 3:5:1. The obtained mixture was made homogeneous by stirring. After distilling off the methanol, 150 ml of water was added to the residue and the mixture was sufficiently kneaded, molded and dried to obtain a mosquito-repellent incense.

The effects of the present invention will be described by the following Test Examples.

The compounds used in the Test Examples as a control are the following comparative compounds (A), (B) and (C). These compounds were also tested according to the same method as the one for the test of compounds of the present invention.

    ______________________________________                                         (A)                                                                                  ##STR224##      (Japanese Patent Publication No. 3898/1968)              (B)                                                                                  ##STR225##      (Japanese Patent Laid-Open No. 98025/1973)               (C)                                                                                  ##STR226##      (J. Agr. Food Chem., 18(1), 57 (1970).                   ______________________________________                                    

TEST EXAMPLE Test Example 1: Effects on resistant and susceptible strains of Nephotettix cincticeps, respectively.

The compounds of the present invention and the comparative compounds were formulated according to the same procedures as the ones described in Formulation Examples 1 and 2 into 20% wettable powders when they were crystal, or into 20% emulsifiable concentration when they were oils, and were used for this test. Further, a 50% emulsifiable concentration of BPMC (2-sec-butylphenylmethylcarbamate) and a 40% emulsifiable concentration of Diazinon (diethyl 2-isopropyl-4-methyl-6-pyrimidinylphosphorothioate) were used as a control.

Method: 5 to 6 rice plants in the tri- to tetra-foliate stages were dipped in 200 ppm chemical solutions for 15 seconds. After air-drying, the plants were placed in a glass cylinder (4.5φ, ×15 cm). Then, ten female adults of Nephotettix cincticeos, susceptible strain (collected in Ageo) and ten of the strain resistant to both organophosphorus and carbamates (collected in Nakagawara and in Izumi) were transferred in the cylinder. After covering with a wire mesh, the cylinder was left in a glass green-house. After 48 hours' treatment, the numbers of live and dead insects were counted to calculate the mortality. The results shown in Table 3 are averages of the two replications.

                  TABLE 3                                                          ______________________________________                                                Mortality (%)                                                           Compound               Resistant  Resistant                                    for      Susceptible   (collected in                                                                             (collected in                                test     (collected in Ageo)                                                                          Nakagawara)                                                                               Izumi)                                       ______________________________________                                         Compound                                                                       No.                                                                             1       100           100        100                                           2       100           100         90                                           3       100            90        100                                           4       100           100        100                                           14      100            90         80                                           23      100            80        100                                           24      100           100        100                                           25      100            90        100                                           29      100           100        100                                           30      100           100        100                                           33      100           100        100                                           36      100           100        100                                           37      100           100        100                                           38      100           100        100                                           39      100           100         90                                           40      100           100         80                                           44      100            90         80                                           46      100           100        100                                           49      100           100         90                                           50      100           100        100                                           97      100           100        100                                          136      100           100        100                                          140      100            90        100                                          141      100           100        100                                          150      100           100        100                                          152      100           100        100                                          156      100           100         90                                          164      100           100        100                                          165      100           100        100                                          169      100           100        100                                          170      100           100        100                                          171      100           100        100                                          172      100           100        100                                          173      100           100        100                                          176      100            80        100                                          177      100           100        100                                          182      100            90         70                                          183      100            80         80                                          185      100           100        100                                          189      100           100        100                                          191      100           100        100                                          192      100            90         80                                          193      100           100        100                                          194      100           100        100                                          195      100           100        100                                          197      100           100         80                                          199      100            90        100                                          201      100           100        100                                          202      100           100        100                                          203      100           100        100                                          204      100            70         70                                          205      100           100         80                                          206      100           100        100                                          208      100            70         90                                          212      100            70         60                                          213      100            80         60                                          214      100           100        100                                          215      100           100        100                                          217      100            80         70                                          220      100           100         70                                          222      100            90         70                                          223      100            70         60                                          230      100            70         60                                          233      100            80         90                                          236      100           100        100                                          237      100           100        100                                          238      100           100        100                                          Control                                                                        A        100            40         20                                          B         90            20         10                                          C         60            0          20                                          Control  100            20         0                                           BPMC                                                                           Diazinon 100            0          30                                          ______________________________________                                    

Test Example 2: Effect on Nilaparvata lugens

The compounds of the present invention and the comparative compounds were formulated according to the same procedures as the ones described in Formulation Examples 1 and 2 into 20% wettable powder or into 20% emulsifiable concentration and tested.

Method: The same procedure described in Test Example 1 were repeated, except that 10 female adults of Nilaparvata lugens were used. 48 hours after treatment, the numbers of live and dead insects were counted to calculate the mortality. The results shown in Table 4 are averages of two replications. Nilaparvata lugens, ten susceptible strains (collected in Kaseda) and ten resistant strains (resistant to both organophosphorus and carbamates, collected in Izumi) was used in this test.

                  TABLE 4                                                          ______________________________________                                                   Mortality (%)                                                                    Susceptible    Resistant                                           Compound for test                                                                          (collected in Kaseda)                                                                         (collected in Izumi)                                ______________________________________                                         Compound No.                                                                    1          100            100                                                  2          100            100                                                  3          100            100                                                  4          100            100                                                  7          100            70                                                   21         100            80                                                   24         100            100                                                  29         100            90                                                   30         100            100                                                  33         100            100                                                  36         100            100                                                  37         100            100                                                  41         100            80                                                   44         100            80                                                   45         100            90                                                   49         100            100                                                  50         100            100                                                 140         100            100                                                 141         100            80                                                  150         100            100                                                 152         100            100                                                 156         100            100                                                 160         100            90                                                  163         100            100                                                 164         100            100                                                 165         100            90                                                  166         100            80                                                  168         100            100                                                 169         100            100                                                 170         100            70                                                  171         100            100                                                 172         100            100                                                 173         100            100                                                 174         100            100                                                 175         100            100                                                 176         100            100                                                 177         100            100                                                 178         100            60                                                  179         100            60                                                  180         100            70                                                  181         100            100                                                 182         100            100                                                 183         100            60                                                  184         100            70                                                  185         100            90                                                  187         100            100                                                 189         100            100                                                 190         100            100                                                 192         100            80                                                  193         100            100                                                 194         100            80                                                  195         100            70                                                  196         100            70                                                  197         100            60                                                  199         100            90                                                  201         100            100                                                 202         100            100                                                 203         100            100                                                 204         100            80                                                  205         100            90                                                  206         100            100                                                 207         100            70                                                  208         100            80                                                  211         100            80                                                  214         100            100                                                 215         100            100                                                 216         100            70                                                  217         100            100                                                 218         100            80                                                  219         100            60                                                  220         100            100                                                 221         100            70                                                  222         100            60                                                  223         100            60                                                  227         100            70                                                  228         100            80                                                  230         100            60                                                  232         100            70                                                  233         100            70                                                  235         100            70                                                  Control                                                                        A            90            40                                                  B            90            30                                                  C            10             0                                                  Control BPMC                                                                               100            10                                                  Diazinon    100            20                                                  ______________________________________                                    

Test Example 3: Effects on larvae of Culex pipiens pallens

The compounds of the present invention and the control were formulated into 0.1% acetone solution and tested.

Method: 199.8 ml of well water was placed in a plastic container having a diameter of 9 cm. Twenty larvae of Culex pipiens pallens (third to fourth instar), collected in Ageo, were transferred into the container. 0.2 ml of the above prepared solution was pipetted into the container to give a chemical solution of 1 ppm. After 24 hours, the numbers of live and dead insects were counted to calculate the mortality. The results shown in Table 5 are averages of the two replications.

                  TABLE 5                                                          ______________________________________                                         Compound for test                                                                              Mortality (%)                                                  ______________________________________                                         Compound No.                                                                    1              100                                                             2              100                                                             3              100                                                             4              100                                                             5              100                                                             6              100                                                             14             100                                                             15             100                                                             16              80                                                             17             100                                                             18             100                                                             19              90                                                             20             100                                                             21             100                                                             22             100                                                             23             100                                                             24             100                                                             25             100                                                             26              80                                                             27              80                                                             28              80                                                             29             100                                                             30             100                                                             31             100                                                             32             100                                                             33             100                                                             34             100                                                             35             100                                                             36             100                                                             37             100                                                             42              80                                                             43              80                                                             44             100                                                             45             100                                                             46             100                                                             47             100                                                             48             100                                                             49             100                                                             50             100                                                             51             100                                                             94             100                                                             95             100                                                             96              80                                                             97             100                                                            136             100                                                            140             100                                                            150             100                                                            152             100                                                            156             100                                                            157             100                                                            158             100                                                            159             100                                                            160             100                                                            161             100                                                            162             100                                                            163             100                                                            164             100                                                            165             100                                                            166             100                                                            169             100                                                            170             100                                                            171             100                                                            172             100                                                            173             100                                                            174             100                                                            176             100                                                            177              80                                                            178             100                                                            180              80                                                            181             100                                                            182             100                                                            183             100                                                            184             100                                                            185             100                                                            186             100                                                            187             100                                                            188              70                                                            189             100                                                            190             100                                                            191             100                                                            192             100                                                            193             100                                                            194             100                                                            195              90                                                            196             100                                                            197             100                                                            198             100                                                            199             100                                                            200             100                                                            201             100                                                            202             100                                                            203             100                                                            204             100                                                            205             100                                                            206             100                                                            207             100                                                            208             100                                                            209             100                                                            210             100                                                            211             100                                                            214             100                                                            215             100                                                            216             100                                                            217             100                                                            218             100                                                            219             100                                                            220             100                                                            221             100                                                            222              70                                                            223              70                                                            224              90                                                            225              70                                                            226              80                                                            227             100                                                            228             100                                                            229             100                                                            230             100                                                            231             100                                                            232             100                                                            233             100                                                            234             100                                                            235             100                                                            236             100                                                            237             100                                                            238             100                                                            239             100                                                            240             100                                                            241             100                                                            Control                                                                        A                70                                                            B                30                                                            C                0                                                             ______________________________________                                    

Test Example 4: Effect on larvae of Plutella xylostella

The compounds of the present invention and the comparative compounds were formulated according to the same procedures as the ones described in Formulation Examples 1 and 2 into 20% wettable powders when they were crystals, or into 20% emulsifiable concentration when they were oils, and were used for this test. Further, a 40% emulsifiable concentration of MEP (0,0-diethyl-O-4-nitro-m-tolyl phosphorothioate) was used as a control.

Method: A cabbage leaf of a medium size cut from a cabbage grown to deca-foliate stage was dipped in a 500 ppm chemical solution for 15 seconds. After air-drying, the leaf was placed in a plastic container having a diameter of 9 cm. 15 larvae (third instar) of Plutella xylostella were transferred into the container. After covering with a lid having several pinholes, the container was left in a green house at 25° C. 48 hours after the treatment, the numbers of live and dead insects were counted to calculate the mortality. The results shown in Table 6 are averages of two replications.

                  TABLE 6                                                          ______________________________________                                         Compound for test                                                                              Mortality (%)                                                  ______________________________________                                         Compound No.                                                                    3              100                                                             4              100                                                            20              100                                                            21              100                                                            23              100                                                            34              100                                                            37              100                                                            Control                                                                        A                10                                                            B                0                                                             C                0                                                             Control MEP      70                                                            ______________________________________                                    

Test Example 5: Effect on adults of Tetranychus urticae

The compounds of the present invention and the controls were formulated according to the same procedures as the ones described in Formulation Examples 1 and 2 into 20% wettable powders when they were crystals, or into 20% emulsifiable concentration when they were oils, and were used for this test.

Method: The primary leaf of a kidney bean which was cultivated in an unglazed pot (diameter: 9 cm) was trimmed to a size of approximately 3 cm×3 cm. 15 female adult mites susceptible to organophosphorus insecticide were transferred onto the leaf carefully using a small brush. The plants were left in a green-house adjusted at 25° C. After one day from the contact with the adults, dead and abnormal mites were taken out of the leaf. The mites on the leaf were dipped in a 400 ppm chemical solution for 10 seconds. After the treatment, the plant was left in the green-house. 48 hours after the treatment, the numbers of live and dead mites were counted under a stereomicroscope to calculate the mortality. The results are shown in Table 7.

                  TABLE 7                                                          ______________________________________                                         Compound for test                                                                              Mortality (%)                                                  ______________________________________                                         Compound No.                                                                    3              100                                                             7              100                                                             8              100                                                             9              100                                                             18             100                                                             24             100                                                            171             100                                                            175             100                                                            176             100                                                            177             100                                                            185             100                                                            ______________________________________                                    

Test Example 6: Effect on the clubroot of tomatoes due to Meloidogine incognita

400 g of soil polluted with Meloidogine incognita was packed in a plastic cup having a diameter of 10 cm. The compounds of the present invention, the comparative compounds and a control compound of DCIP [bis(2-chloromethylethyl)ether] were formulated according to the same procedure as the one described in Formulation Example 3 into 1% dusts. 40% mg of each dust was applied to the soil, followed by entire mixing. 15 seeds (variety: Ponte Rosa) were sown per cup.

40 days after the chemical treatment, the tomatoes were digged up and examined for damage due to chemicals and clubroot index. The results are shown in Table 7.

The clubroot index was calculated by the following expression: ##EQU1##

A: Number of tomato seedlings having at least 31 clubroots.

B: Number of tomato seedlings having 21 to 30 clubroots.

C: Number of tomato seedlings having 11 to 20 clubroots.

D: Number of tomato seedlings having 1 to 10 clubroots. The results are shown in Table 8.

                  TABLE 8                                                          ______________________________________                                         Compound for test                                                                             Clubroot index                                                                             Phytotoxicity                                       ______________________________________                                         Compound No.                                                                    3             45          no                                                   4             48          no                                                   7             42          no                                                  23             13          no                                                  29             40          no                                                  32             20          no                                                  43             39          no                                                  Control (C)    78          no                                                  Control DCIP   83          no                                                  Untreated      100         --                                                  ______________________________________                                    

Test Example 7: Effect on larvae of Anomala cuprea in the soil

50 grams of chemical solution diluted with water, were fully mixed with 100 grams of dried soil containing dried leaf mold, and the treated soil was transferred to a plastic cup together with five 1st instar larvae of Cupreous chafer, Anomala cuprea and was kept in temperature controlled room (25° C.). After 2 days, the number of live and dead larvae was counted and mortalities were calculated. The results are shown in Table 9.

                  TABLE 9                                                          ______________________________________                                                        Mortality (%)                                                                  Concentration in soil                                           Compound for test                                                                               100 ppm   10 ppm                                              ______________________________________                                         Compound No.                                                                    3               100       100                                                  4               100        80                                                  10              100       100                                                  14              100        80                                                  29              100       100                                                  30              100       100                                                  31              100       100                                                  32              100       100                                                  34              100       100                                                  36              100       100                                                  37              100       100                                                  46              100       100                                                  48              100       100                                                 150              100       100                                                 152              100       100                                                 164              100       100                                                 165              100       100                                                 169              100       100                                                 170              100       100                                                 171              100        80                                                 173              100       100                                                 176              100        80                                                 182              100       100                                                 185              100        80                                                 189              100       100                                                 190              100        60                                                 193              100       100                                                 206              100       100                                                 Untreated         0         0                                                  ______________________________________                                     

What we claim is:
 1. A compound of the formula: ##STR227## wherein Ar is ##STR228## R¹ is C₃ -C₅ -alkyl unsubstituted or substituted with F or Cl, C₃ -C₆ -cycloalkyl, C₃ -C₆ -cycloalkylmethyl, R² is CH₃, CH₂ Cl or C₂ H₅ and x is 0, 1 or
 2. 2. A compound of the formula (I) according to claim 1, wherein Ar is ##STR229## R¹ n-C₃ H₇, iso-C₃ H₇, sec-C₄ H₉, iso-C₄ H₉, cyclopentyl or cyclopropylmethyl, R² is CH₃, CH₂ CI or C₂ H₅, x is 0, 1 or
 2. 3. A compound of the formula (I) according to claim 2 which is selected from the group consisting of one of the following formulas: ##STR230##
 4. An insecticidal, acaricidal or nematicidal composition which comprises an effective amount of a compound of the formula: ##STR231## wherein Ar is ##STR232## R¹ is C₃ -C₅ -alkyl unsubstituted or substituted with F or Cl, C₃ -C₆ -cycloalkylmethyl, R² is CH₃, CH₂ CI or C₂ H₅ and x is 0, 1 or
 2. 5. A method for killing insect pests, acarids or nematodes, which comprises applying an effective amount of a compound of the formula: ##STR233## where Ar is ##STR234## R¹ is C₃ -C₅ -alkyl unsubstituted or substituted with F or Cl, C₃ -C₆ -cycloalkyl or C₃ -C₆ -cycloalkylmethyl, R² is CH₃, CH₂ Cl or C₂ H₅ and x is 0, 1 or
 2. 